CN101971303B - Method for Sr-Ti-o-based film formation and storage medium - Google Patents
Method for Sr-Ti-o-based film formation and storage medium Download PDFInfo
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- CN101971303B CN101971303B CN2008801031673A CN200880103167A CN101971303B CN 101971303 B CN101971303 B CN 101971303B CN 2008801031673 A CN2008801031673 A CN 2008801031673A CN 200880103167 A CN200880103167 A CN 200880103167A CN 101971303 B CN101971303 B CN 101971303B
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- 238000000034 method Methods 0.000 title claims description 80
- 238000003860 storage Methods 0.000 title description 47
- 230000015572 biosynthetic process Effects 0.000 title description 26
- 239000007800 oxidant agent Substances 0.000 claims abstract description 78
- 239000002994 raw material Substances 0.000 claims description 158
- 229910003077 Ti−O Inorganic materials 0.000 claims description 102
- 210000000713 mesentery Anatomy 0.000 claims description 95
- 230000001590 oxidative effect Effects 0.000 claims description 77
- 239000000758 substrate Substances 0.000 claims description 77
- 229910004356 Ti Raw Inorganic materials 0.000 claims description 66
- 238000007254 oxidation reaction Methods 0.000 claims description 41
- 230000003647 oxidation Effects 0.000 claims description 40
- 230000008676 import Effects 0.000 claims description 32
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 255
- 239000007789 gas Substances 0.000 description 148
- 239000003085 diluting agent Substances 0.000 description 35
- 238000000746 purification Methods 0.000 description 34
- 238000002425 crystallisation Methods 0.000 description 28
- 239000012159 carrier gas Substances 0.000 description 25
- 238000005755 formation reaction Methods 0.000 description 25
- 230000007246 mechanism Effects 0.000 description 24
- 239000004065 semiconductor Substances 0.000 description 24
- 230000008025 crystallization Effects 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 229910002367 SrTiO Inorganic materials 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 15
- 230000005587 bubbling Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 238000000137 annealing Methods 0.000 description 11
- 239000011261 inert gas Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000002309 gasification Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000003672 processing method Methods 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 230000003028 elevating effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000011112 process operation Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910017083 AlN Inorganic materials 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000000391 smoking effect Effects 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010058490 Hyperoxia Diseases 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000000222 hyperoxic effect Effects 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
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- C23C16/45525—Atomic layer deposition [ALD]
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- C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
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Abstract
A film is formed so that the atomic ratio of Sr to Ti, i.e., Sr/Ti, in the film is not less than 1.2 and not more than 3. The film is then annealed in an atmosphere containing not less than 0.001% and not more than 80% of O2 at 500 DEG C or above. An SrO film forming step and a TiO film forming step are repeated a plurality of times so that a sequence, in which a plurality of SrO film forming steps or/and a plurality of TiO film forming steps are performed continuously, is included. When Sr is oxidized after the adsorption of Sr, O3 and H2O are used as an oxidizing agent.
Description
Technical field
The present invention relates to form SrTiO
3Film build method and the storage medium of the Sr-Ti-O film of the Sr-Ti-O mesenterys such as film.
Background technology
In semiconductor equipment, integrated circuit highly integrated growing is even also require to reduce the area of memory cell and increase memory capacity for DRAM.For this requirement, the capacitor of MIM (metal-insulator-metal type) structure attracts attention.As the capacitor of this mim structure, use strontium titanates (SrTiO
3) etc. high dielectric constant material as dielectric film (dielectric film).
The SrTiO that uses as the DRAM capacitor
3The film build method of film, the in the past following method of many employings: use organic Sr raw material and organic Ti raw material, use O
3Gas etc. adopt the ALD method to carry out method (for example, the people such as J.H.Lee, " the Plasma enhancedatomic layer deposition of SrTiO of film forming as oxidant
3Thin films with Sr (tmhd)
2And Ti (i-OPr)
4" J.Vac.Scl.Techno1.A20 (5), Sep/Oct 2002).
Yet, when wanting to adopt such method to form thin film, even at Sr: Ti=1: in 1 the stoichiometric composition, also can produce the problem that is difficult for crystallization and so on even anneal after film forming according to the kind of substrate.Therefore the Sr-Ti-O based material wishes to carry out crystallization owing to dielectric constant under amorphous state is low.
On the other hand, in the ALD method, make by carrying out Sr raw material-purification-oxidant-purification the SrO film forming stage, carry out Ti raw material-purification-oxidant-purification and make the stage of TiO film forming alternately repeat to carry out film forming, but in the method, according to the combination of raw material, the composition after appearance generation absorption obstruction etc., the film forming is not the situation of required composition sometimes.
And then, in the ALD method, set the service time of each raw material and oxidant for time that thickness reaches capacity, but use O
3During as oxidant, kind according to the organic Sr compound that is used as the Sr raw material needs the long period till arriving saturation point, the thickness of per 1 circulation when reaching capacity is 0.3~0.4nm, very thick, required SrO can't be carried out the problem of film forming when having.
Summary of the invention
The object of the invention is to: provide stably to make SrTiO
3The film build method of the Sr-Ti-O mesentery of crystallization.
Other purposes of the present invention are: the film build method that can make Sr and Ti reach the Sr-Ti-O mesentery of required ratio is provided.
Further other purposes of the present invention are: provide oxidant is promptly arrived supply with saturation point, can form required SrO and obtain the film build method of the Sr-Ti-O mesentery of good Sr-Ti-O mesentery.
Other purpose of the present invention is: the storage medium that the program that stores these methods of execution is provided.
According to the 1st viewpoint of the present invention, a kind of film build method of Sr-Ti-O mesentery is provided, be the film build method that forms the Sr-Ti-O mesentery of Sr-Ti-O mesentery at substrate, comprising: placement substrate in container handling; Heated substrates; Under the state that substrate is heated, with the ratio Sr/Ti of the Sr in the film and Ti by atomicity than the mode of counting 1.2~3, gasiform Ti raw material, gasiform Sr raw material and gasiform oxidant are imported in the above-mentioned container handling, in above-mentioned container handling, the Sr-Ti-O mesentery is formed on the substrate; At the O that contains 0.001%~80%
2Atmosphere in, more than 500 ℃ the substrate after the film forming is being annealed.
In above-mentioned the 1st viewpoint, preferably the ratio Sr/Ti with the Sr in the film and Ti carries out film forming by atomicity than the mode of counting 1.4~1.9.In addition, when the film forming of above-mentioned Sr-Ti-O mesentery, following SrO film can be become mem stage become mem stage respectively to carry out repeatedly with the TiO film, described SrO film becomes mem stage to comprise: import gasiform Sr raw material in the above-mentioned container handling and Sr is adsorbed on the substrate, import gasiform oxidant in the above-mentioned container handling and make the Sr oxidation, then will purify in the container handling; Described TiO film becomes mem stage to comprise: import gasiform Ti raw material in the above-mentioned container handling and Ti is adsorbed on the substrate, import gasiform oxidant in the above-mentioned container handling and make the oxidation of Ti film, then will purify in the container handling.And then, can become mem stage repeatedly to carry out continuously the mode of such order a plurality of above-mentioned SrO films to comprise, repeatedly carry out above-mentioned SrO film and become mem stage to become mem stage with above-mentioned TiO film.
The 2nd viewpoint of the present invention provides a kind of film build method of Sr-Ti-O mesentery, is the film build method that forms the Sr-Ti-O mesentery of Sr-Ti-O mesentery at substrate, comprising: placement substrate in container handling; Heated substrates; Under the state that substrate is heated, gasiform Ti raw material, gasiform Sr raw material and gasiform oxidant are imported in the above-mentioned container handling, in above-mentioned container handling, the Sr-Ti-O mesentery is formed on the substrate.When the film forming of above-mentioned Sr-Ti-O mesentery, become mem stage or a plurality of TiO film to become mem stage or the two repeatedly to carry out continuously the mode of such order a plurality of SrO films to comprise, become mem stage to become mem stage respectively to carry out repeatedly with the TiO film following SrO film, described SrO film becomes mem stage to comprise: import gasiform Sr raw material in the above-mentioned container handling and Sr is adsorbed on the substrate, import gasiform oxidant in the above-mentioned container handling and make the Sr oxidation, then will purify in the container handling; Described TiO film becomes mem stage to comprise: import gasiform Ti raw material in the above-mentioned container handling and Ti is adsorbed on the substrate, import gasiform oxidant in the above-mentioned container handling and make the oxidation of Ti film, then will purify in the above-mentioned container handling.
In above-mentioned the 2nd viewpoint, can will repeatedly carry out above-mentioned SrO film become mem stage after, repeatedly carry out setting group (set) that above-mentioned TiO film becomes mem stage repeatedly, for example, can with carry out 2 above-mentioned SrO films become mem stage after, carry out setting group that 2 above-mentioned TiO films become mem stage repeatedly.
According to the 3rd viewpoint of the present invention, a kind of film build method of Sr-Ti-O mesentery is provided, be the film build method that forms the Sr-Ti-O mesentery of Sr-Ti-O mesentery at substrate, comprising: placement substrate in container handling; Heated substrates; Under the state that substrate is heated, gasiform Ti raw material, gasiform Sr raw material and gasiform oxidant are imported in the above-mentioned container handling, in above-mentioned container handling, the Sr-Ti-O mesentery is formed on the substrate;
When the film forming of above-mentioned Sr-Ti-O mesentery, become mem stage to become mem stage respectively to carry out repeatedly with the TiO film following SrO film, and use O
3And H
2O is as above-mentioned oxidant, and described SrO film becomes mem stage to comprise: import gasiform Sr raw material in the above-mentioned container handling and Sr is adsorbed on the substrate, import gasiform oxidant in the above-mentioned container handling and make the Sr oxidation, then will purify in the container handling; Described TiO film becomes mem stage to comprise: import gasiform Ti raw material in the above-mentioned container handling and Ti is adsorbed on the substrate, import gasiform oxidant in the above-mentioned container handling and make the oxidation of Ti film, then will purify in the container handling.
In above-mentioned the 3rd viewpoint, as above-mentioned Sr raw material, can use the Sr compound with cyclopentadienyl group, be typically Sr (C
5(CH
3)
5)
2In this case, in the above-mentioned oxidant, H
2O has the function with Sr and cyclopentadienyl group cut-out, O
3Has the function that forms SrO.
According to the 4th viewpoint of the present invention, a kind of storage medium is provided, to move on computers, store the storage medium be used to the program that is controlled to film device, above-mentioned control program is when carrying out, make the above-mentioned film formation device of computer control, so that carry out the film build method of following Sr-Ti-O mesentery, the film build method of described Sr-Ti-O mesentery is the film build method that forms the Sr-Ti-O mesentery of Sr-Ti-O mesentery at substrate, comprising: placement substrate in container handling; Heated substrates; Under the state that substrate is heated, with the ratio Sr/Ti of the Sr in the film and Ti by atomicity than the mode of counting 1.2~3, gasiform Ti raw material, gasiform Sr raw material and gasiform oxidant are imported in the above-mentioned container handling, in above-mentioned container handling, the Sr-Ti-O mesentery is formed on the substrate; At the O that contains 0.001%~80%
2Atmosphere in, more than 500 ℃ the substrate after the film forming is being annealed.
According to the 5th viewpoint of the present invention, a kind of storage medium is provided, to move on computers, store the storage medium be used to the program that is controlled to film device, above-mentioned control program is when carrying out, make the above-mentioned film formation device of computer control, so that carry out the film build method of following Sr-Ti-O mesentery, the film build method of described Sr-Ti-O mesentery is the film build method that forms the Sr-Ti-O mesentery of Sr-Ti-O mesentery at substrate, comprising: placement substrate in container handling; Heated substrates; Under the state that substrate is heated, gasiform Ti raw material, gasiform Sr raw material and gasiform oxidant are imported in the above-mentioned container handling, in above-mentioned container handling, the Sr-Ti-O mesentery is formed on the substrate.Wherein, when the film forming of above-mentioned Sr-Ti-O mesentery, become mem stage or a plurality of TiO film to become mem stage or the two repeatedly to carry out continuously the mode of such order a plurality of SrO films to comprise, become mem stage to become mem stage respectively to carry out repeatedly with the TiO film following SrO film, described SrO film becomes mem stage to comprise: import gasiform Sr raw material in the above-mentioned container handling and Sr is adsorbed on the substrate, import gasiform oxidant in the above-mentioned container handling and make the Sr oxidation, then will purify in the container handling; Described TiO film becomes mem stage to comprise: import gasiform Ti raw material in the above-mentioned container handling and Ti is adsorbed on the substrate, import gasiform oxidant in the above-mentioned container handling and make the oxidation of Ti film, then will purify in the above-mentioned container handling.
According to the 6th viewpoint of the present invention, a kind of storage medium is provided, to move on computers, store the storage medium be used to the program that is controlled to film device, above-mentioned control program is when carrying out, make the above-mentioned film formation device of computer control, so that carry out the film build method of Sr-Ti-O mesentery, the film build method of described Sr-Ti-O mesentery is the film build method that forms the Sr-Ti-O mesentery of Sr-Ti-O mesentery at substrate, comprising: placement substrate in container handling; Heated substrates; Under the state that substrate is heated, gasiform Ti raw material, gasiform Sr raw material and gasiform oxidant are imported in the above-mentioned container handling, in above-mentioned container handling, the Sr-Ti-O mesentery is formed on the substrate.Wherein, when the film forming of above-mentioned Sr-Ti-O mesentery, become mem stage to become mem stage respectively to carry out repeatedly with the TiO film following SrO film, and use O
3And H
2O is as above-mentioned oxidant, and described SrO film becomes mem stage to comprise: import gasiform Sr raw material in the above-mentioned container handling and Sr is adsorbed on the substrate, import gasiform oxidant in the above-mentioned container handling and make the Sr oxidation, then will purify in the container handling; Described TiO film becomes mem stage to comprise: import gasiform Ti raw material in the above-mentioned container handling and Ti is adsorbed on the substrate, import gasiform oxidant in the above-mentioned container handling and make the oxidation of Ti film, then will purify in the container handling.
According to the present invention, carry out film forming by atomicity than the mode of counting 1.2~3 with the ratio Sr/Ti of the Sr in the film and Ti after, at the O that contains 0.001%~80%
2Atmosphere in, annealing more than 500 ℃, even the film of 7~20nm also can stably make SrTiO thus
3Crystallization.That is, carry out film forming with the many compositions of Sr after, at O
2Existence under anneal, Ti moves to the surface and forms SrTiO thus
3Crystallization is even therefore film also can make it crystallization.
In addition, according to the present invention, owing to becoming mem stage or a plurality of TiO film to become mem stage or the two repeatedly to carry out continuously the mode of such order a plurality of SrO films to comprise, repeatedly carrying out the SrO film becomes mem stage to become mem stage with the TiO film, even therefore the combination as raw material can produce the such situation of absorption obstruction, also can repeat a plurality of identical one-tenth mem stages during avoid such absorption to hinder, can obtain the Sr-Ti-O mesentery of required composition.
And then, according to the present invention, owing to repeatedly carrying out the SrO film when becoming mem stage to become mem stage to obtain the Sr-Ti-O mesentery with the TiO film, use O
3And H
2O is as oxidant, therefore oxidant reached capacity rapidly, can form required SrO and obtains good Sr-Ti-O mesentery.That is, only use O
3As oxidant, use for example Sr (C of specific organic Sr compound as the Sr raw material
5(CH
3)
5)
2The time owing to having the effect that after the key of the organic moiety of organic Sr compound that will use as the Sr raw material cuts off, forms SrO scatteredly, therefore need the long period to cutting off till reaching capacity, but by and use H
2O, H
2O is breaking at the key of organic moiety hardly, mainly contains the cut-out that helps Sr and organic moiety, therefore just reaches capacity in early days.And, thereafter by making O
3Effect just can form required SrO.In addition, only use H
2O forms Sr (OH) during as oxidant
2, can bring bad result, but pass through at H
2Make O after the O
3Effect can obtain good SrO.
Description of drawings
[Fig. 1] expression can be used for implementing the profile that the summary of film formation device of the film build method of Sr-Ti-O mesentery of the present invention consists of.
[Fig. 2] is illustrated in the same technique Sr-Ti-O mesentery with 5nm on the Si substrate and carries out film forming, the figure of X-ray diffractogram when annealing at Ru (50nm)/TiN (30nm)/Si.
[Fig. 3] expression is adjusted and to be created conditions and the Sr/Ti of film forming is the figure of the X-ray diffractogram of 3 kinds of Sr-Ti-O mesenterys of 0.7,1.1,2.4.
[Fig. 4] expression for take the Sr-Ti-O mesentery of the mode film forming of Sr/Ti as 2.4 at O
2Concentration is the situation of annealing in 10% the atmosphere and at O
2Concentration is lower than the situation of annealing in the atmosphere of 10ppm, relatively the figure of the X-ray diffractogram of Sr-Ti-O mesentery.
[Fig. 5] expression utilizes the figure of the film forming order of ALD method.
The figure of the order when [Fig. 6] expression forms the Sr-Ti-O mesentery with the ALD method and the ratio of components of thickness and Sr/Ti.
[Fig. 7] expression with the SrO film with step 1~4 become mem stage repeat 2 times, then the TiO film with step 5~8 becomes mem stage to repeat 2 times as a setting group, the figure of the order when this setting group is repeated to make the Sr-Ti-O mesentery 20 times and the ratio of components of thickness and Sr/Ti.
[Fig. 8] expression with the SrO film with step 1~4 become mem stage repeat 2 times, then the TiO film with step 5~8 becomes mem stage to repeat 3 times as a setting group, the figure of the order when this setting group is repeated to make the Sr-Ti-O mesentery 20 times and the ratio of components of thickness and Sr/Ti.
The figure of the relation between (the De one ズ) time that gives of [Fig. 9] expression Sr raw material and Ti raw material and the thickness of SrO film and TiO film monofilm.
[Figure 10] represents O
3Give the figure of the relation between the thickness of time and SrO film and TiO film monofilm.
The figure of the relation between the clarification time when the suction purification has been carried out in [Figure 11] expression and the thickness of SrO film and TiO film monofilm.
[Figure 12] expression has also imposed the O that suction purifies
3Give the figure of the relation between the thickness of time and SrO film and TiO film monofilm.
The figure of the film forming order of [Figure 13] expression the 3rd execution mode of the present invention.
The figure of other examples of gas supply mechanism is processed in [Figure 14] expression.
Embodiment
Below, with reference to accompanying drawing, contrast figure limit, limit describes embodiments of the present invention.
Fig. 1 is the profile that the summary of the expression film formation device that can be used in the film build method of implementing Sr-Ti-O mesentery of the present invention consists of.Film formation device 100 shown in Figure 1 has such as the container handling 1 that is shaped to cylindric or case shape by aluminium etc., is provided with in container handling 1 for the mounting table 3 of mounting as the semiconductor wafer W of processed substrate.Mounting table 3 aluminium compounds such as carbon source materials, aluminium nitride about by thick 1mm etc. consists of.
At the outer circumferential side of mounting table 3, form for example division wall 13 made of aluminum of the cylinder shape hold up from container handling 1 bottom, and make its upper end for example bend to the L word shape and form bend 14 to horizontal direction.Like this, by the division wall 13 of cylinder shape is set, in the inner face side formation inert gas purge chamber 15 of mounting table 3.Be in above the bend 14 on the top identical in fact plane with mounting table 3, from the periphery of mounting table 3 separately, insert in this gap and to be connected with pitman 12.3 (only showing 2 illustrated example) support arms 4 that mounting table 3 is extended out from the upper inside wall of dividing wall 13 support.
Below mounting table 3, in the mode of giving prominence to upward from the support component 6 of ring-type the many for example lifting bolts 5 of 3 L word shapes (only showing 2 illustrated example) are set.Support component 6 can utilize the elevating lever 7 of being arranged to run through container handling 1 bottom to carry out lifting, and elevating lever 7 utilizes the driver 10 that is positioned at container handling 1 below to move up and down.The part corresponding with lifting bolt 5 in mounting table 3, be provided with inserting hole 8 in the mode that runs through mounting table 3, utilize driver 10 and by elevating lever 7 and support component 6 lifting bolt 5 is risen, can make thus lifting bolt 5 insert logical these inserting holes 8 and semiconductor wafer W is lifted.Elevating lever 7 covers with bellows 9 to the insertion portion of container handling 1, prevents extraneous gas 1 interior intrusion from this insertion portion to container handling.
For the circumference that keeps semiconductor wafer W and be fixed in mounting table 3 sides, be provided with such as the clamping ring parts 11 such as pottery systems such as aluminium nitride along the roughly ring-type of the contour shape of discoideus semiconductor wafer W at the circumference of mounting table 3.Clamping ring parts 11 are connected with above-mentioned support component 6 by pitman 12, carry out integratedly lifting with lifting bolt 5.Lifting bolt 5, pitman 12 etc. are formed by potteries such as aluminium oxide.
Below interior all sides of ring-type clamping ring parts 11, form a plurality of contact protrusions 16 that configure in equally spaced mode roughly along circumferencial direction, during clamping, connect above the lower surface of contact protrusion 16 and the circumference of semiconductor wafer W and with its extruding.In addition, the diameter of contact protrusion 16 is about 1mm, about high about 50 μ m of being, uses gap 17 in the 1st gas purification of this part formation ring-type during clamping.In addition, the lap of interior all sides of the circumference of semiconductor wafer W and clamping ring parts 11 during clamping (the 1st gas purification with the flow path length in gap 17) L1 for number mm about.
The peripheral part of clamping ring parts 11 is used gap 18 in the top of the upper end bend 14 of dividing wall 13 in this 2nd gas purification that forms ring-type.The 2nd gas purification for for example about 500 μ m, is large about the 10 times wide cut of wide cut than the 1st gas purification usefulness gap 17 with the wide cut in gap 18.The lap of the circumference of clamping ring parts 11 and bend 14 (the 2nd gas purification flow path length in gap 18) is for for example roughly about 10mm.Thus, the inert gas in the inert gas purge chamber 15 can be from two gaps 17,18 go out to processing the space effluent.
In the bottom of container handling 1, be provided with the inert gas feed mechanism 19 of the 15 supply inert gases to above-mentioned inert gas purge chamber.This gas supply mechanism 19 has: be used for inert gas for example Ar gas to the inert gas purge chamber 15 gas nozzles 20 that import, be used for supplying with as the Ar gas supply source 21 of the Ar gas of inert gas and from Ar gas supply source 21 to gas nozzle the 20 gas pipe arrangements 22 that import the Ar gas.In addition, be provided with mass flow controller 23 and switch valve 24,25 as flow controller at gas pipe arrangement 22.As inert gas, can replace Ar gas with He gas etc.
Position under the mounting table 3 of the bottom of container handling 1 is provided with airtightly by what the infrared ray permeable materials such as quartz formed and sees through window 30, thereunder, is provided with the heating chamber 31 of case shape to surround the mode that sees through window 30.In this heating chamber 31, a plurality of heating lamps 32 as heater are installed doubling as the rotating platform 33 of using for speculum.The rotary engine 34 that rotating platform 33 is located at heating chamber 31 bottoms by the rotating shaft utilization is rotated.Therefore, thereby the infrared ray of emitting from heating lamp 32 sees through window 30 irradiation mounting table 3 below be heated.
In addition, the circumference in container handling 1 bottom is provided with exhaust outlet 36, and exhaust outlet 36 is connected with the blast pipe 37 that is connected with not shown vacuum pump.So, carry out exhaust by this exhaust outlet 36 and blast pipe 37, can will maintain the vacuum degree of regulation in the container handling 1.In addition, at the sidewall of container handling 1, be provided with the family of power and influence 38 of I/O port 39 and the switch I/O port 39 of I/O semiconductor wafer W.
On the other hand, at the top of the container handling 1 relative with mounting table 3, be provided with for the shower nozzle 40 to container handling 1 interior importing such as unstrpped gas.Shower nozzle 40 is such as being made of aluminium etc., has the discoid body 41 of formation of the 41a that has living space in inside.Be provided with gas introduction port 42 at the top of body 41.Gas introduction port 42 is connected with by its pipe arrangement 51 and supplies with as SrTiO
3The processing gas supply mechanism 50 of the necessary processing gas of film forming of the Sr-Ti-O mesentery that film is such.In the bottom of a body 41, spread all over whole ground and dispose a plurality of gas jetting holes 43 of emitting to the processing space in the container handling 1 for the gases that will supply with in the body to the end 41, thereby gas can be released to whole of semiconductor wafer W.In addition, the space 41a in a body 41 is equipped with the diffuser plate 44 with a plurality of gas dispersion hole 45, can be to the surface of semiconductor wafer W supply gas more equably.And then, in the sidewall of container handling 1 with the sidewall of shower nozzle 40 in and dispose in the face relative with wafer of gas jetting hole 43, be respectively equipped with for the cartridge heater 46,47 of adjusting temperature, thereby sidewall, the showerhead that contacts with gas can be remained on set point of temperature.
Processing gas supply mechanism 50 has storage and stays the Sr raw material storage part 52 of Sr raw material, storage to stay the Ti raw material storage part 53 of Ti raw material, supplies with the oxidant supply source 54 of oxidant and be used for the diluent gas supply source 55 of the diluent gass such as supply argon gas of the gas in the dilution process container 1.
The pipe arrangement 57 that the pipe arrangement 51 that is connected with shower nozzle 40 is connected with the pipe arrangement 56 that extends out from Sr raw material storage part 52, extend out from Ti raw material storage part 53, from the pipe arrangement 58 that oxidant supply source 54 extends out, pipe arrangement 51 is connected with above-mentioned diluent gas supply source 55.Pipe arrangement 51 is provided with mass flow controller (MFC) 60 and the switch valve 61,62 before and after it as flow controller.In addition, pipe arrangement 58 is provided with mass flow controller (MFC) 63 and the switch valve 64,65 before and after it as flow controller.
Sr raw material storage part 52 is situated between to be connected with by pipe arrangement 67 and supplies with the carrier gas supply source 66 that Ar etc. is used for carrying out the carrier gas of bubbling.Pipe arrangement 67 is provided with mass flow controller (MFC) 68 and the switch valve 69,70 before and after it as flow controller.In addition, Ti raw material storage part 53 also is situated between and is connected with the carrier gas supply source 71 of supplying with the carrier gas such as Ar by pipe arrangement 72.Pipe arrangement 72 is provided with mass flow controller (MFC) 73 and the switch valve 74,75 before and after it as flow controller.Sr raw material storage part 52, Ti raw material storage part 53 are respectively equipped with heater 76,77.So, store up the Sr raw material that stays and store up the Ti raw material that the stays mode with bubbling under by the states of these heaters 76,77 heating at Ti raw material storage part 53 at Sr raw material storage part 52 and be fed into container handling 1.In addition, although do not illustrate, the pipe arrangement of supplying with under the state with Sr raw material, Ti material gasification also is provided with heater.
Side wall upper part at container handling 1 is provided with the NF that imports as clean air
3The clean air introduction part 81 of gas.Be connected with supply NF in this clean air introduction part 81
3The pipe arrangement 82 of gas is provided with remote plasma generating unit 83 at this pipe arrangement 82.So, in this remote plasma generating unit 83, the NF that is situated between and is supplied with by pipe arrangement 82
3Gas by plasma, it is fed in the container handling 1, will clean in the container handling 1 thus.In addition, also the remote plasma generating unit can be set directly over shower nozzle 40, be situated between by shower nozzle 40 supplying clean gases.In addition, can use F
2Replace NF
3, can not use remote plasma, and use CIF
3Deng the thermal cleaning that carries out without plasma.
And, as required, be used to from the indication at user interface 91 etc. general arbitrarily processing method from storage part 92, breathe out and make process controller 90 carry out, under the control of process controller 90, carry out required processing at film formation device 100 thus.
Then, for using the film formation device that consists of in the above-described manner to become the execution mode of membrane processing method to describe.
The<the 1 execution mode 〉
In the 1st execution mode, at first, open the family of power and influence 38,, be positioned on the mounting table 3 in the semiconductor wafer W input processing container 1 from I/O port 39.Window 30 was emitted and seen through to mounting table 3 in advance by heating lamp 32 infrared heating utilizes this heat that semiconductor wafer W is heated.And, for example supply with Ar gas as diluent gas from diluent gas supply source 55 with the flow of 100~800mL/sec (sccm), be situated between by exhaust outlet 36 and blast pipe 37 container handling 1 interior exhaust by not shown vacuum pump simultaneously, thus the pressure vacuum in the container handling 1 be vented to about 39~665Pa.The heating-up temperature of the semiconductor wafer W of this moment is set at for example 200~400 ℃.
And, the flow that dilutes with gas, for example Ar gas is made as 100~500mL/sec (sccm), simultaneously the pressure in the container handling 1 is controlled at into film pressure 6~266Pa, the film forming that beginning is actual.In addition, the pressure adjustment in the container handling 1 is undertaken by the automatic pressure controller (APC) of being located at blast pipe 37.
In the present embodiment, when actual film forming, repeatedly carrying out following SrO film becomes mem stage to become mem stage with the TiO film, then by annealing to form the Sr-Ti-O mesentery, described SrO film becomes mem stage to be: by with the Sr raw material supplying to processing operation (step 1) in the container 1, supplying in the container handling 1 with the operation (step 2) of container handling 1 interior purification, with oxidant and the Sr raw material decomposed and the operation (step 3) of oxidation, the operation (step 4) of container handling 1 interior purification is formed thin SrO film; Described TiO film becomes mem stage to be: by the Ti raw material supplying is supplied in the container handling 1 to the operation (step 6) of processing operation (step 5) in the container 1, remove with container handling 1 interior purification and with unnecessary Ti raw material, with oxidant the Ti raw material decomposed and the operation (step 7) of oxidation, container handling 1 interior purification is formed thin TiO film with the operation (step 8) that unnecessary oxidant is removed.The membrance casting condition of control this moment, with the ratio Sr/Ti of the Sr in the film and Ti by atomicity than the mode of counting 1.2~3, at the O that contains 0.001%~80%
2Atmosphere in, the condition more than 500 ℃ carries out the annealing after the film forming.In addition, become in the mem stage at above-mentioned TiO film, the in fact oxygen quantitative change in the film and become TiOx (x is 1~2), but for convenient, be labeled as " TiO film ".
According to the surface state of using substrate etc., when forming the film of Sr-Ti-O system, can crystallization even sometimes carry out film forming with stoichiometric composition yet.For example, when substrate surface is Ru, than being easier to crystallization, but at the metal nitride films such as Si, TiN, Al
2O
3, ZrO
2Deng being difficult for crystallization on the amorphous oxide film.Fig. 2 illustrates: with same technique, form the Sr-Ti-O mesentery of 5nm at the Si substrate, and at Ru (50nm)/TiN (30nm)/Si, be the TiN film that the Si substrate forms 30nm, and then form the Ru film of 50nm thereon and carry out film forming on the structure that obtains, at O
2Content is less than 0.001% N
2Under the atmosphere with 600 ℃, X-ray diffractogram when the condition of 120min is annealed.Adopting the Sr/Ti ratio of the upper film of Si of XRF (fluorescent X-ray method) mensuration is 1.35.According to Fig. 2, although the Sr-Ti-O mesentery on the Si has no the SrTiO of expression crystallization
3The peak, but the Sr-Ti-O mesentery on the Ru 32.5 the degree near obtain SrTiO
3(110) peak, the as can be known easy crystallization on Ru of Sr-Ti-O mesentery.But, by adopting method of the present invention, even substrate surface is the material that the Sr-Ti-O mesenterys such as Si, TiN are difficult for crystallization, even and the film of 7~20nm and so on, also can stably make SrTiO
3Crystallization.That is, carry out film forming with the many compositions of specific Sr after, at O
2Anneal under existing, Ti moves to the surface and forms SrTiO thus
3Crystallization is even therefore thin film also can make it crystallization.
At this, Sr/Ti is by the atomicity ratio, and less than 1.2 o'clock, the Ti on surface became too much, is difficult to occur crystallization on the film surface, surpassed at 3 o'clock, and the absolute magnitude of Ti becomes very few, thereby still is difficult to occur crystallization.The more preferably scope of Sr/Ti is 1.4~1.9.
Fig. 3 is that expression is adjusted and to be created conditions and film forming obtains on the Si substrate, adopt XRF to measure Sr/Ti is the figure of the X-ray diffractogram of 3 kinds of Sr-Ti-O mesenterys of 0.7,1.1,2.4.In addition, for these films, after film forming, at O
2Concentration is to anneal in 600 ℃ under 10% the atmosphere.As shown in the drawing, satisfy 2.4 film of above-mentioned scope for Sr/Ti, there is expression SrTiO
3SrTiO is confirmed at the peak of crystallization
3Crystallization.Relative therewith, exceed above-mentioned extraneous 0.7,1.1 film for Sr/Ti, there is not obvious peak, confirm that film does not have crystallization.In addition, Sr/Ti is that the thickness of 3 kinds of Sr-Ti-O mesenterys of 0.7,1.1,2.4 is respectively 5.5nm, 6.6nm, 8.2nm.
The O in the atmosphere when annealing after the film forming why
2Content is made as 0.001%~80%, is because less than 0.001% the time, the hypoxgia in the film, SrTiO
3Crystallization is difficult to produce, and hyperoxia when surpassing 80% can make the significantly oxidations such as the Ru, the TiN that become the substrate of Sr-Ti-O mesentery, Si.In addition, why making temperature is more than 500 ℃, is in order to supply with the necessary heat energy of crystallization.
Fig. 4 is expression for to adopt XRF to measure Sr/Ti be 2.4 and carry out Sr-Ti-O mesentery that film forming obtains at O at Si
2Concentration is the situation of annealing under 10% the atmosphere and at O
2Concentration is lower than the situation of annealing under the atmosphere of 3ppm, the figure that the X-ray diffractogram of Sr-Ti-O mesentery is compared.As shown in the drawing, at O
2Concentration is in 10% the atmosphere, has expression SrTiO
3SrTiO is confirmed at the peak of crystallization
3Crystallization.Relative therewith, at O
2Concentration is lower than in the atmosphere of 3ppm, does not have obvious peak, confirms that film does not have crystallization.
Then, concrete creating conditions described.
For Sr/Ti being made as suitable value, at least one that can enumerate in selection to Sr raw material, Ti raw material, oxidant, flow, service time, the order adjusted during film forming.
About order, typically can adopt as shown in Figure 5, alternately repeat the SrO film and become mem stage to become the method for the ALD of mem stage with the TiO film.But, in the present embodiment owing to essential forming the many compositions of Sr, so continuous several times to repeat the mode that above-mentioned SrO film becomes mem stage to carry out also be effective.
In step 1, for the Sr raw material, from utilize heater 76 be heated to Sr raw material storage part 52 about 150~230 ℃, in the mode of bubbling by shower nozzle 40 with the Sr raw material supplying to processing in the container 1.As the Sr raw material, can use the organic Sr compound that in the past used as this raw material, for example can preferably use Sr (DPM)
2, Sr (C
5(CH
3)
5)
2Deng.Wherein, can use preferably that steam forces down, the Sr (C of processing ease
5(CH
3)
5)
2When supplying with the Sr raw material, for example flow out Ar gas as diluent gas from the flow of diluent gas supply source 55 about with 100~500mL/min (sccm), for example flow out Ar gas as carrier gas from the flow of carrier gas supply source 66 about with 50~500mL/min (sccm).In addition, the supply (step 1) of Sr raw material for example carry out about 0.1~20sec during.
In the operation with the oxidation of Sr raw material of step 3, oxidant is fed in the container handling 1 by shower nozzle 40 from oxidant supply source 54.Thus, the Sr raw material that adsorbs on the semiconductor wafer W surface is decomposed and is oxidized, forms the SrO film.When supplying with oxidant (step 3), under the state that flows out about diluent gass, for example Ar gas 100~500mL/min (sccm) from diluent gas supply source 55, for example carry out about 0.1~20sec during.As oxidant, can preferably use O
3Gas, O
2Gas, H
2O or O
2The plasma of gas.Use O
3Gas uses ozone generator as oxidant supply source 54, with 50~200g/Nm during as oxidant
3About flow supply with.At this moment, may be used O
2Gas, the O of this moment
2The flow of gas is about 100~1000mL/min (sccm).Use H
2O is during as oxidant, and its flow preferably is made as about 2~50mL/min (sccm).
In step 5, from utilize heater 77 carried out the Ti raw material storage part 53 of heating, in the mode of bubbling by shower nozzle 40 with the Ti raw material supplying to processing in the container 1.As the Ti raw material, can preferably use Ti (OiPr)
4, Ti (OiPr)
2(DPM)
2Deng.At this moment, the heating-up temperature of Ti raw material storage part 53 is used Ti (OiPr)
4The time be about 50~70 ℃, use Ti (OiPr)
2(DPM)
2The time be about 150~230 ℃.When supplying with the Ti raw material, for example flow out Ar gas as diluent gas from the flow of diluent gas supply source 55 about with 100~500mL/min (sccm), for example flow out Ar gas as carrier gas from the flow of carrier gas supply source 71 about with 100~500mL/min (sccm).In addition, the supply (step 5) of Ti raw material for example carry out about 0.1~20sec during.
Oxidation operation (step 7) behind the Ti raw material supplying is: under the condition identical with step 3, flowing out under the state of diluent gas from diluent gas supply source 55, oxidant is supplied in the container handling 1 by shower nozzle 40 from oxidant supply source 54.Thus, the Ti raw material is decomposed and is oxidized, forms the TiO film.
Can be by Sr unstrpped gas, Ti unstrpped gas or the oxidant before stopping to supply with in step 2,4,6,8 cleaning procedure, and will supply in the container handling from diluent gas, for example Ar gas of diluent gas supply source 55 and carry out.At this moment, gas flow is about 200~1000mL/min (sccm).In addition, do not aspirate to circulated gases yet.This operation for example carry out about 0.1~20sec during.
With the SrO film of step 1~4 become the TiO of mem stage and step 5~8 become mem stage repeat more than 20 times, for example 100 times, can form with the thickness of regulation Sr/Ti by atomicity than the Sr-Ti-O mesentery of counting 1.2~3.
So form after the film, supply with for example O from oxidant supply source 54 with the regulation flow
2Gas, make positively oxidation of film after, all gas is stopped, to carrying out vacuum draw in the container handling, then, utilize conveying arm with the output of the semiconductor wafer W in the container handling 1.
Then, at the O of condition as described above
2Under the atmosphere semiconductor wafer W is annealed.Annealing can use RTA (short annealing, Rapid Thermal Anneal), common heating furnace to carry out.
The control of the valve in the above order, mass flow controller etc. be based on storage in the storage part 92 method, utilize process controller 90 to carry out.
Then, the embodiment that carries out actual film forming based on present embodiment is shown.
In the device of above-mentioned Fig. 1, regulate the lamp source, be 320 ℃ of film-forming temperatures with the Temperature Setting of mounting table, use the arm of transfer robot with in the 200mmSi wafer input processing container, form the Sr-Ti-O mesentery.As the Sr raw material, use Sr (C
5(CH
3)
5)
2, hold it in the container that is heated to 160 ℃, Ar gas is supplied to container handling as carrier gas and with Bubbling method.As the Ti raw material, use Ti (OiPr)
4, hold it in the container that is heated to 45 ℃, similarly Ar gas is supplied to container handling as carrier gas and with Bubbling method.In addition, as oxidant, make O
2Gas with 500mL/min (sccm), make N
2The concentration that gas generates by ozone generator take 0.5mL/min (sccm) is as 180g/m
3O
3
Then, after being arranged on the Si wafer on the mounting table with arm, make the Ar diluent gas cross 30sec with the traffic flow of 300mL/min (sccm), simultaneously make the Si wafer be warmed up to film-forming temperature with the pressure of 133Pa (1Torr) after, adopt above-mentioned step 1~8 to carry out film forming.In addition, chip temperature is 290 ℃.
The Sr raw material supplying operation of step 1 is: the flow of Ar carrier gas is made as 50mL/min (sccm), the flow of Ar diluent gas is made as 200mL/min (sccm), during the pressure control mechanism of container handling 1 entirely opened state with exhaust and carry out 10sec, for the purification of step 2, carry out 10sec with aspiration phases (obstructed gas body ground is opened the pressure control mechanism of container handling 1 and the state that carries out exhaust entirely) during.
The oxidation operation of the Sr raw material of step 3 is: use above-mentioned O
3Gas is as oxidant, during the pressure control mechanism of container handling 1 is entirely opened state with exhaust and carried out 10sec.The purification of step 4 is carried out during the 10sec with aspiration phases.
The Ti raw material supplying operation of step 5 is: the flow of Ar carrier gas is made as 200mL/min (sccm), the flow of Ar diluent gas is made as 200mL/min (sccm), during the pressure control mechanism of container handling 1 is entirely opened state with exhaust and carried out 10sec.Purification and the step 2 of step 6 are same, carry out 10sec with aspiration phases during.
The oxidation operation of the Ti raw material of step 7 and the purification of step 8 with step 3 and the identical condition of step 4 under carry out.
Through step 1~8, the pressure control mechanism of container handling 1 is opened entirely, pressure in the container handling is according to the having or not of through-flow gas, flow and difference, and as an example: step 1 is that 0.36Torr, step 2,4,6,8 are that 0Torr, step 3 are that 0.52Torr, step 5 are 0.39Torr.
Then, the SrO film that repeats 2 step 1~4 become mem stage, after the TiO film that then repeats 2 step 5~8 becomes the such order of mem stage to repeat 25 times, make O
2Gas is crossed 10sec with the traffic flow of 300mL/min (sccm), simultaneously pressure is controlled at 40Pa (0.3Torr), then under stopping the state of gas, be evacuated in container handling and keep 100sec, then the Si wafer is exported from container handling.
Thickness to the Sr-Ti-O film that forms by above such order is measured, and the result is 13nm.Measure this film with XRD (X-ray diffraction method), the result has no the peak of expression crystallization.Measure the composition of this film with XRF (fluorescent X-ray method), Sr/Ti is than counting 2.2 by the atomicity ratio as a result.
Then, will be formed with the Si substrate input RTA device of above-mentioned Sr-Ti-O mesentery, at the O that contains 0.2%
2The N of gas
2Apply 600 ℃ RTA under the gas normal pressure atmosphere, then, adopt XRD (X-ray diffraction method) to measure, the result sees SrTiO
3Peak crystallization, confirm SrTiO
3Crystallization.
The<the 2 execution mode 〉
In the 2nd execution mode, identical with the 1st execution mode, at first, open the family of power and influence 38, from I/O port 39 with in the semiconductor wafer W input processing container 1, be positioned in advance with heating lamp 32 and carried out on the mounting table 3 of heating, semiconductor wafer W is heated to set point of temperature, for example 200~400 ℃.Then, for example supply with Ar gas as diluent gas from diluent gas supply source 55 with the flow of 100~800mL/sec (sccm), be situated between by exhaust outlet 36 and blast pipe 37 container handling 1 interior exhaust by not shown vacuum pump simultaneously, thus the pressure vacuum in the container handling 1 be vented to about 6~665Pa.Then, the flow that dilutes with gas, for example Ar gas is made as 100~500mL/sec (sccm), simultaneously the pressure in the container handling 1 is controlled at into film pressure 13~266Pa, the film forming that beginning is actual.
In the present embodiment, when actual film forming, repeatedly carrying out following SrO film becomes mem stage to become mem stage to form the Sr-Ti-O mesentery with the TiO film, comprising a plurality of SrO films being become mem stage or a plurality of TiO film become mem stage or the two repeatedly to carry out continuously such order, described SrO film becomes mem stage to be: by with the Sr raw material supplying to the operation (step 1) of processing in the container 1, operation (step 2) with container handling 1 interior purification, supply to oxidant in the container handling 1 and the Sr raw material decomposed and the operation (step 3) of oxidation, the operation (step 4) of container handling 1 interior purification is formed thin SrO film; Described TiO film becomes mem stage to be: by with the Ti raw material supplying to process operation (step 5) in the container 1, with the operation (step 6) of container handling 1 interior purification, supply to oxidant in the container handling 1 and the Ti raw material decomposed and the operation (step 7) of oxidation, the operation (step 8) of container handling 1 interior purification formed thin TiO film.
In above-mentioned ALD method, according to the combination of raw material occur sometimes producing absorption hinder wait, composition after the film forming is not the situation of required composition, but by adopting such order, repeat a plurality of SrO films become mem stage or a plurality of TiO film become mem stage during can avoid absorption to hinder, can form the composition close with required composition.In addition, by adopting such method, can form the Sr-Ti-O mesentery of the required composition from Sr composition how to the many compositions of Ti.
Use Sr (C
5(CH
3)
5)
2As the Sr raw material, use Ti (OiPr)
4As the Ti raw material, as shown in Figure 6, adopt ALD method in the past, become the TiO film of mem stage and above-mentioned steps 5~8 to become mem stage alternately to repeat 20 times the SrO film of above-mentioned steps 1~4, form the Sr-Ti-O mesentery (SrO: TiO=1: 1), as a result thickness be 4.5nm, Sr/Ti ratio of components by atomicity than count 0.4, Sr lacks.That is the absorption that, has produced the Sr raw material hinders.
Relative therewith, use same raw material, as shown in Figure 7, become mem stage to repeat 2 times the SrO film of above-mentioned steps 1~4, then the TiO film with above-mentioned steps 5~8 becomes mem stage to repeat 2 times, should the setting group repeat 20 times and form the Sr-Ti-O mesentery (SrO: TiO=2: 2), thickness is that the ratio of components of 8.7nm, Sr/Ti is counted 1.0, is roughly stoichiometric composition by the atomicity ratio as a result.Confirm thus, by with the one-tenth mem stage of same materials repeatedly, can eliminate this film forming obstruction.
In addition, as shown in Figure 8, become mem stage to repeat 2 times the SrO film of above-mentioned steps 1~4, then the TiO film with above-mentioned steps 5~8 becomes mem stage to repeat 3 times, as a setting group, should the setting group repeat 20 times and form the Sr-Ti-O mesentery (SrO: TiO=2: 3), thickness is that the ratio of components of 8.6nm, Sr/Ti counts 0.7 by the atomicity ratio as a result, confirmed by the one-tenth mem stage that changes same materials repeat number, can obtain required ratio of components.
About the particular content of step 1~8, identical with the 1st execution mode.Then, adopt as described above to become mem stage and/or TiO film to become mem stage after continuously repeatedly such order forms the Sr-Ti-O mesentery SrO film, supply with for example O from oxidant supply source 54 with the regulation flow
2Gas makes positively oxidation of film.Then, all gas is stopped, after vacuumizing in the container handling, utilize conveying arm with the output of the semiconductor wafer W in the container handling 1.
The control of the valve in the above order, mass flow controller etc. is identical with the 1st execution mode, is based on that the method adopting process controller 90 stored in the storage part 92 carries out.
Then, the embodiment that carries out actual film forming based on present embodiment is shown.
In the device of above-mentioned Fig. 1, regulate the lamp source, be 320 ℃ of film-forming temperatures with the Temperature Setting of mounting table, use the arm of transfer robot with in the 200mmSi wafer input processing container, form the Sr-Ti-O mesentery.Use Sr (C
5(CH
3)
5)
2As the Sr raw material, hold it in the container that is heated to 160 ℃, supply to container handling take Ar gas as carrier gas and with Bubbling method.Use Ti (OiPr)
4As the Ti raw material, hold it in the container that is heated to 45 ℃, similarly supply to container handling take Ar gas as carrier gas and with Bubbling method.In addition, as oxidant, make O
2Gas with 500mL/min (sccm), make N
2The concentration that gas generates by ozone generator take 0.5mL/min (sccm) is as 180g/m
3O
3
Then, utilize after arm is arranged at the Si wafer on the mounting table, make the Ar diluent gas cross 30sec with the traffic flow of 300mL/min (sccm), simultaneously make the Si wafer be warmed up to film-forming temperature with the pressure of 133Pa (1Torr) after, carry out film forming by above-mentioned step 1~8.In addition, chip temperature is 290 ℃.
The Sr raw material supplying operation of step 1 is: the flow that makes the Ar carrier gas is 50mL/min (sccm), the flow that makes the Ar diluent gas is 200mL/min (sccm), during the pressure control mechanism of container handling 1 entirely opened state with exhaust and carry out 10sec, in the purification of step 2, carry out 10sec with aspiration phases during.
The oxidation operation of the Sr raw material of step 3 is: use above-mentioned O
3Gas is as oxidant, during the pressure control mechanism of container handling 1 is entirely opened state with exhaust and carried out 10sec.The purification of step 4 is carried out during the 10sec with aspiration phases.
The Ti raw material supplying operation of step 5 is: the flow that makes the Ar carrier gas is 200mL/min (sccm), make the flow of Ar diluent gas is 200mL/min (sccm), during the pressure control mechanism of container handling 1 entirely opened state with exhaust and carry out 10sec, the purification of step 6 is identical with step 2, carry out 10sec with aspiration phases during.
The oxidation operation of the Ti raw material of step 7 and the purification of step 8, with step 3 and the identical condition of step 4 under carry out.
Then, become the TiO film of mem stage and step 5~8 to become mem stage alternately to repeat 20 times the SrO film of step 1~4 after, pressure is maintained 40Pa (0.3Torr), cross O with the traffic flow of 300mL/min (sccm) simultaneously
2Gas 20sec, then with the state that stopped gas with being evacuated in the container handling and keeping 20sec, then the Si wafer is exported from container handling.
Thickness to the Sr-Ti-O film that forms by above such order is measured, and the result is 4nm.Measure the composition of this film with XRF (fluorescent X-ray method), Sr/Ti is than counting 0.5 by the atomicity ratio as a result.
On the other hand, the SrO film that repeats 2 step 1~4 become mem stage, after the TiO film that then repeats 2 step 5~8 becomes the such order of mem stage to repeat 10 times, cross O with the traffic flow of 300mL/min (sccm)
2Gas 10sec is controlled at pressure 40Pa (0.3Torr) simultaneously, then is evacuated in container handling under the state that has stopped gas and keeps 100sec, then the Si wafer is exported from container handling.Measure the thickness of formed Sr-Ti-O film, the result is 5nm.Measure the composition of this film with XRF (fluorescent X-ray method), Sr/Ti is than counting 1.0 by the atomicity ratio as a result.
Like this, confirmed according to the present invention: by adopting the order that repeats continuously identical one-tenth mem stage, can not adsorbed the impact of obstruction, obtain the Sr-Ti-O mesentery of required composition.
The<the 3 execution mode 〉
In the 3rd execution mode, identical with the 1st execution mode, at first, open the family of power and influence 38, from I/O port 39 with in the semiconductor wafer W input processing container 1, load on the mounting table 3 of having carried out in advance heating with heating lamp 32, semiconductor wafer W is heated to set point of temperature, for example 200~400 ℃.Then, for example supply with Ar gas as diluent gas from diluent gas supply source 55 with the flow of 100~800mL/sec (sccm), utilize not shown vacuum pump to be situated between by exhaust outlet 36 and blast pipe 37 container handling 1 interior exhaust, thus the pressure vacuum in the container handling 1 is vented to about 39~665Pa.Then, the flow that dilutes with gas, for example Ar gas is made as 100~500mL/sec (sccm), simultaneously the pressure in the container handling 1 is controlled at into film pressure 39~266Pa, begin actual film forming.
In the present embodiment, when actual film forming, become mem stage to become mem stage to form the Sr-Ti-O mesentery with the TiO film by repeatedly carrying out following SrO film, and use O
3And H
2O is as oxidant, and described SrO film becomes mem stage to be: by with the Sr raw material supplying to process operation (step 1) in the container 1, with the operation (step 2) of container handling 1 interior purification, supply to oxidant in the container handling 1 and the Sr raw material decomposed and the operation (step 3) of oxidation, the operation (step 4) of container handling 1 interior purification formed thin SrO film; Described TiO film becomes mem stage to be: by with the Ti raw material supplying to process operation (step 5) in the container 1, with the operation (step 6) of container handling 1 interior purification, supply to oxidant in the container handling 1 and the Ti raw material decomposed and the operation (step 7) of oxidation, the operation (step 8) of container handling 1 interior purification formed thin TiO film.
In the ALD method, the service time of each raw material and oxidant is configured to the time that thickness reaches capacity, but uses O
3During as oxidant, the kind according to the organic Sr compound that uses as the Sr raw material needs the long period till arriving saturation point, and the thickness of per 1 circulation when reaching capacity is 0.3~0.4nm, and is very thick, sometimes required SrO can't be carried out film forming.That is, only use O
3As oxidant, use for example Sr (C of specific organic Sr compound
5(CH
3)
5)
2During as the Sr raw material, work owing to forming SrO after the cut-out of the key in the organic moiety of organic Sr compound that will use as the Sr raw material, therefore till cut-out reaches capacity, need the long period.
Relative therewith, by using H
2O in situation the about hardly key in the organic moiety being cut off, mainly contains the cut-out that helps Sr and organic moiety as oxidant, therefore just reaches capacity in early days.But, if only use H
2O then can form Sr (OH) as oxidant
2And bring bad result.Therefore, in the present embodiment, utilize H
2O makes O after Sr and organic moiety are cut off
3Act on and formation SrO, obtain thus good SrO film.
Below, this respect is elaborated.
Fig. 9 is that Sr (C is used in expression
5(CH
3)
5)
2As Sr raw material, use Ti (OiPr)
4The figure of the relation between the monofilm thickness of the time that gives during as the Ti raw material, each raw material and SrO film and TiO film.As shown in the drawing, each raw material reaches capacity about 5sec, and for thickness, the thickness of SrO film is thicker than the TiO film.In addition, the chip temperature of this moment is 290 ℃.
Figure 10 is that O is used in expression
3During as oxidant, O
3The time that gives and the figure of the relation between the monofilm thickness of SrO film and TiO film.As shown in the drawing, the TiO film just reaches capacity at short notice, even SrO film 60sec is also unsaturated.In addition, the Sr raw material of this moment and the time that gives of Ti raw material are 10sec, and chip temperature is made as 290 ℃.
Figure 11 is the figure that expression will purify the relation between the monofilm thickness when carrying out with Smoking regime, clarification time and SrO film and TiO film.As shown in the drawing, carry out even will purify with Smoking regime, the thickness of SrO film also can be along with the increase of clarification time thickening.And the result that will carry out when suction purifies also adds fashionable O
3The time that gives and the relation between the monofilm thickness of SrO film and TiO film be shown in Figure 12, even confirmed to change purification method, the thickness that also can't suppress the SrO film can be along with O
3Give the time and thickening.
Why film thickens like this, if it is elongated to be considered to oxidization time, then uses O
3During with organic Sr raw material oxidation, the organic moiety that exists at organic Sr raw material, (C for example
5(CH
3)
5)
2Can't separate with Sr fast and the decomposition of this organic moiety is being carried out, when the giving of Sr raw material next time, the cause that the Sr raw material adsorbs more.
Therefore, in the present embodiment, the H that use can be preferentially cut off the key of Sr and organic moiety
2O is as oxidant, isolate organic moiety to a certain degree after, supply with O
3And oxidation is carried out.
Then, concrete creating conditions described.
About order, typically adopt to become mem stage to become the method for the alternately repeated ALD of mem stage with the TiO film SrO film.
About the particular content of step 1~8, the oxidant in the oxidation operation of step 3 is different with the order of oxidation operation, identical with the 1st execution mode.
In the present embodiment, the step 3 with the oxidation of Sr raw material is: use at first H
2The O steam carries out oxidation processes (step 3-1) as oxidant, then uses O
3Carry out oxidation processes (step 3-2).Step 3-1 is with for example H
2The flow of O is to carry out about 0.1~5sec about 2~50mL/min (sccm).Step 3-2 for example uses ozone generator as oxidant supply source 54, with 50~200g/Nm
3About flow supply with.This moment can be with O
2Gas and usefulness, the O of this moment
2The flow of gas is about 100~1000mL/min (sccm).This step 3-2 carries out about 0.1~10sec.Can flow through simultaneously H
2O and O
3, also can be with O
2Dew point adjust to 0~40 ℃ and make it to flow through ozone generator.In addition, can also H will be made
2And O
2Flowing through the material that remote plasma forms uses as oxygen source.
The concrete order of present embodiment as shown in figure 13.
Then, after as described above the SrO film being become mem stage to become mem stage alternately to repeat with the TiO film and forming the Sr-Ti-O mesentery, supply with for example O from oxidant supply source 54 with the regulation flow
2Gas makes positively oxidation of film.Then, whole gas is stopped, behind vacuum draw in the container handling, utilize conveying arm with the output of the semiconductor wafer W in the container handling 1.
The control of the valve in the above order, mass flow controller etc. is identical with the 1st execution mode, is based on that the method for storing in the storage part 92 undertaken by process controller 90.
Then, the embodiment that has carried out actual film forming based on present embodiment is shown.
In the device of above-mentioned Fig. 1, regulate the lamp source, be 320 ℃ of film-forming temperatures with the Temperature Setting of mounting table, use the arm of transfer robot with in the 200mmSi wafer input processing container, form the Sr-Ti-O mesentery.Use Sr (C
5(CH
3)
5)
2As the Sr raw material, hold it in the container that is heated to 160 ℃, supply to container handling take Ar gas as carrier gas and with Bubbling method.Use Ti (OiPr)
4As the Ti raw material, hold it in the container that is heated to 40 ℃, similarly supply to container handling take Ar gas as carrier gas and with Bubbling method.In addition, as oxidant, use: with H
2O is heated to 40 ℃, and the H that carries out flow control with the high temperature mass flow controller that is heated to 50 ℃
2O, and make O
2Gas with 500mL/min (sccm), make N
2The concentration that gas generates by ozone generator take 0.5mL/min (sccm) is as 180g/m
3O
3
Then, after being arranged at the Si wafer on the mounting table with arm, make the Ar diluent gas cross 30sec with the traffic flow of 300mL/min (sccm), simultaneously make the Si wafer be warmed up to film-forming temperature with the pressure of 133Pa (1Torr) after, carry out film forming by above-mentioned step 1~8.In addition, chip temperature is 290 ℃.
The Sr raw material supplying operation of step 1 is: take the flow of Ar carrier gas as 50mL/min (sccm), take the flow of Ar diluent gas as 200mL/min (sccm), during the pressure control mechanism of container handling 1 entirely opened state with exhaust and carry out 10sec, in the purification of step 2, carry out 10sec with aspiration phases during.
The operation with the oxidation of Sr raw material of step 3 is: at first, 3-1 makes H as step
2The processing 3sec of O steam flow, then, 3-2 makes O as step
3During the processing 5sec of circulation.The state that these operations open the pressure control mechanism of container handling 1 entirely with exhaust carries out.The purification of step 4 is carried out during the 10sec with aspiration phases.
The Ti raw material supplying operation of step 5 is: take the flow of Ar carrier gas as 200mL/min (sccm), take the flow of Ar diluent gas as 200mL/min (sccm), during the pressure control mechanism of container handling 1 entirely opened state with exhaust and carry out 10sec, the purification of step 6 is identical with step 2, carry out 10sec with aspiration phases during.
The oxidation operation of the Ti raw material of step 7 is: use above-mentioned O
3Gas carries out during the 10sec the interior aspiration phases that forms of container handling as oxidant.The purification of step 8 with the identical condition of step 4 under carry out.
Then, become the TiO film of mem stage and step 5~8 to become mem stage alternately to repeat 50 times the SrO film of step 1~4 after, make O
2Gas is crossed 20sec with the traffic flow of 300mL/min (sccm), and pressure is controlled at 40Pa (0.3Torr), then is evacuated in container handling under the state that has stopped gas and keeps 20sec, then the Si wafer is exported from container handling.Measure the thickness of formed Sr-Ti-O film, the result is 12nm.Measure the C amount of film with X ray photoelectricity spectrum analysis (XPS), the result is below detection limit (1%).That is the organic moiety of, having confirmed the Sr raw material does not almost have oxidized dose of decomposition.
In addition, the invention is not restricted to above-mentioned execution mode, can carry out various restrictions.
For example, in above film formation device, use to adopt the bubbling mode to carry out the processing gas supply mechanism 50 of raw material supplying, but also can carry out the processing gas supply mechanism 50 of raw material supplying ' replace it with gasifier with so as shown in figure 14.Process gas supply mechanism 50 ' have: so that the Sr raw material be dissolved in the state of solvent store up the Sr raw material storage part 52 that stays ' so that the Ti raw material be dissolved in the state of solvent store up the Ti raw material storage part 53 that stays ', supply with the oxidant supply source 54 of oxidant ' and gasifier 101 of making Sr raw material and Ti material gasification.From Sr raw material storage part 52 ' be provided with pipe arrangement 102 to gasifier 101, from Ti raw material storage part 53 ' be provided with pipe arrangement 103 to gasifier 101.Utilize force feed gas or pump etc. with liquid from Sr raw material storage part 52 ' and Ti raw material storage part 53 ' supply to gasifier 101.Pipe arrangement 102 is provided with as the liquid quality flow controller (LMFC) 104 of flow controller and the switch valve 105,106 before and after it.In addition, pipe arrangement 103 is provided with liquid quality flow controller (LMFC) 107 and the switch valve 108,109 before and after it.Sr raw material storage part 52 ', Ti raw material storage part 53 ' be respectively equipped with heater 76 ', 77 '.So, the Sr raw material of the Sr raw material storage part 52 ' state that stays, be dissolved in solvent that stores up, Ti raw material with the Ti raw material storage part 53 ' state that stays, be dissolved in solvent that stores up, by these heaters 76 ', 77 ' be heated to set point of temperature, supply to gasifier 101 with pump, gas force feed etc. with liquid condition.In addition, although not shown, the pipe arrangement of circulation Sr raw material, Ti raw material also is provided with heater.
Gasifier 101 be connected with the above-mentioned pipe arrangement 51 that arrives shower nozzle 40 '.Gasifier 101 is connected with the pipe arrangement 111 that extends out from the carrier gas supply source 110 of the carrier gas such as supply Ar gas, carrier gas is supplied to gasifier 101, for example will in gasifier 101, be heated to the Sr raw material of 100~200 ℃ and gasification and Ti raw material by pipe arrangement 51 ' and shower nozzle 40 import in the container handling 1.Pipe arrangement 111 is provided with mass flow controller (MFC) 112 and the switch valve 113,114 before and after it as flow controller.From oxidant supply source 54 ' to pipe arrangement 51 ' be provided with pipe arrangement 115, with oxidant from pipe arrangement 115 through pipe arrangements 51 ' and shower nozzle 40 to container handling 1 interior importing.Pipe arrangement 115 is provided with mass flow controller (MFC) 116 and the switch valve 117,118 before and after it as flow controller.Gas supply mechanism 50 ' also have supply with the diluent gas supply source 55 that is used for diluent gass such as argon gas that the gas in the container handling 1 is diluted '.This diluent gas supply source 55 ' be provided with arrive pipe arrangement 51 ' pipe arrangement 119, will dilute with argon gas from pipe arrangement 119 through pipe arrangements 51 ' with shower nozzle 40 to container handling 1 interior importing.Pipe arrangement 119 is provided with mass flow controller (MFC) 120 and the switch valve 121,122 before and after it as flow controller.
When using gas supply mechanism 50 ' formations Sr-Ti-O mesentery, except the Ti raw material supplying of the Sr raw material supplying of above-mentioned steps 1 and step 5 is different, basically similarly implement the film forming processing with above-mentioned order.
In the Sr of step 1 raw material supplying, Sr raw material storage part 52 ' in make the Sr raw material be dissolved in the solvents such as octane, cyclohexane.The concentration of this moment is preferably 0.05~1mol/L.Its supply is heated to 100~200 ℃ gasifier 101 and makes it gasification.This moment from diluent gas supply source 55 ' diluent gas, the flow of for example Ar gas be 100~500mL/min (sccm), coming the carrier gas of self contained gas supply source 110, the flow of for example Ar gas is about 100~500mL/min (sccm).When then, this operation being carried out supply with above-mentioned bubbling same degree during.
In the Ti of step 1 raw material flows, Ti raw material storage part 53 ' in make the Ti raw material be dissolved in the solvents such as octane, cyclohexane, and be transported to and make it gasification in the gasifier 101 that is heated to 150~230 ℃.The concentration of this moment is preferably 0.05~1mol/L.This moment from diluent gas supply source 55 ' diluent gas, the flow of for example Ar gas be 100~500mL/min (sccm), coming the carrier gas of self contained gas supply source 110, the flow of for example Ar gas is about 100~500mL/min (sccm).When then, this operation being carried out supply with above-mentioned bubbling same degree during.
In addition, in the above-described embodiment, show the device that utilizes lamp heating and processed substrate is heated as film formation device, but also can be the device that utilizes resistance heater to heat.In addition, show in the above-described embodiment and use semiconductor wafer as the situation of processed substrate, but be not limited to semiconductor wafer, also can use FPD with other substrates such as glass substrates.
And then, in the above-described embodiment, show in film forming the example of the pressure control mechanism of container handling being opened entirely and carrying out exhaust more, but also can be not make pressure control mechanism work and remain on required pressure in 13~266Pa scope.In addition, show when purifying the not example of the formation aspiration phases of circulated gases, but also can be to make inert gas about 100~1000mL/min (sccm), for example making under the logical state of Ar air-flow pressure control mechanism is opened to carry out exhaust entirely, perhaps pressure is being remained on 20~266Pa.
And then, even the respective embodiments described above appropriate combination is implemented also within the scope of the invention.
Utilizability on the industry
Sr-Ti-O mesentery of the present invention is effective as the electrode in the capacitor of mim structure.
Claims (5)
1. the film build method of a Sr-Ti-O mesentery is the film build method that forms the Sr-Ti-O mesentery of Sr-Ti-O mesentery at substrate, comprising:
Placement substrate in container handling,
Heated substrates,
Under the state that substrate is heated, with the ratio Sr/Ti of the Sr in the film and Ti by atomicity than the mode of counting 2.2~3, with gasiform Ti raw material, gasiform Sr (C
5(CH
3)
5)
2Raw material and gasiform oxidant import in the described container handling, in described container handling, the Sr-Ti-O mesentery be formed on the substrate,
At the O that contains 0.001%~80%
2Atmosphere in, more than 500 ℃ the substrate after the film forming is being annealed, the Ti in the described Sr-Ti-O mesentery moves to the surface.
2. the film build method of a Sr-Ti-O mesentery is the film build method that forms the Sr-Ti-O mesentery of Sr-Ti-O mesentery at substrate, comprising:
Placement substrate in container handling,
Heated substrates,
Under the state that substrate is heated, gasiform Ti raw material, gasiform Sr raw material and gasiform oxidant are imported in the described container handling, in described container handling, the Sr-Ti-O mesentery is formed on the substrate,
When the film forming of described Sr-Ti-O mesentery, with comprise become mem stage to become mem stage with the TiO film SrO film each carries out the mode of at least 2 such order continuously, become mem stage to become mem stage respectively to carry out repeatedly with the TiO film following SrO film,
Described SrO film becomes mem stage to comprise: with gasiform Sr (C
5(CH
3)
5)
2Raw material imports in the described container handling and Sr is adsorbed on the substrate, imports gasiform oxidant in the described container handling and makes the Sr oxidation, then will purify in the container handling;
Described TiO film becomes mem stage to comprise: import gasiform Ti raw material in the described container handling and Ti is adsorbed on the substrate, import gasiform oxidant in the described container handling and make the oxidation of Ti film, then will purify in the described container handling.
3. the film build method of Sr-Ti-O mesentery according to claim 2, will repeatedly carry out described SrO film become mem stage after, repeatedly carry out setting group that described TiO film becomes mem stage repeatedly.
4. the film build method of Sr-Ti-O mesentery according to claim 3, will carry out 2 described SrO films become mem stage after, carry out setting group that 2 described TiO films become mem stage repeatedly.
5. the film build method of a Sr-Ti-O mesentery is the film build method that forms the Sr-Ti-O mesentery of Sr-Ti-O mesentery at substrate, comprising:
Placement substrate in container handling,
Heated substrates,
Under the state that substrate is heated, gasiform Ti raw material, gasiform Sr raw material and gasiform oxidant are imported in the described container handling, in described container handling, the Sr-Ti-O mesentery is formed on the substrate,
When the film forming of described Sr-Ti-O mesentery, become mem stage to become mem stage respectively to carry out repeatedly with the TiO film following SrO film,
Described SrO film becomes mem stage to comprise: with gasiform Sr (C
5(CH
3)
5)
2Raw material imports in the described container handling and Sr is adsorbed on the substrate, with gasiform H
2O imports in the described container handling and makes the Sr oxidation, then, and with gasiform O
3Import in the described container handling and make the Sr oxidation, then will purify in the container handling;
Described TiO film becomes mem stage to comprise: import gasiform Ti raw material in the described container handling and Ti is adsorbed on the substrate, with gasiform O
3Import in the described container handling and make the oxidation of Ti film, then will purify in the container handling.
Applications Claiming Priority (3)
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JP2007-228745 | 2007-09-04 | ||
JP2007228745 | 2007-09-04 | ||
PCT/JP2008/065706 WO2009041219A1 (en) | 2007-09-04 | 2008-09-02 | Method for sr-ti-o-base film formation and recording medium |
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CN101971303A CN101971303A (en) | 2011-02-09 |
CN101971303B true CN101971303B (en) | 2013-05-01 |
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US (1) | US8679913B2 (en) |
JP (1) | JP5678252B2 (en) |
KR (2) | KR101217419B1 (en) |
CN (1) | CN101971303B (en) |
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WO (1) | WO2009041219A1 (en) |
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WO2010141668A2 (en) * | 2009-06-03 | 2010-12-09 | Intermolecular, Inc. | Methods of forming strontium titanate films |
JP5761724B2 (en) * | 2012-01-24 | 2015-08-12 | 文彦 廣瀬 | Thin film forming method and apparatus |
CN103839875B (en) * | 2012-11-21 | 2017-08-22 | 北京北方微电子基地设备工艺研究中心有限责任公司 | A kind of lining treatment system |
JP5956972B2 (en) * | 2012-12-21 | 2016-07-27 | 東京エレクトロン株式会社 | Deposition method |
JP2020122206A (en) * | 2019-01-31 | 2020-08-13 | 東京エレクトロン株式会社 | Control method of substrate treatment apparatus and substrate treatment apparatus |
JP7454915B2 (en) | 2019-04-11 | 2024-03-25 | 東京エレクトロン株式会社 | Processing equipment and processing method |
KR102639298B1 (en) * | 2020-10-30 | 2024-02-20 | 삼성에스디아이 주식회사 | Organic metal compound, composition for depositing thin film comprising the organic metal compound, manufacturing method for thin film using the composition, thin film manufactured from the composition, and semiconductor device including the thin film |
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JP2003059921A (en) * | 2001-07-30 | 2003-02-28 | Applied Materials Inc | Method of forming insulator film and method of manufacturing capacitor member |
US7416994B2 (en) * | 2005-06-28 | 2008-08-26 | Micron Technology, Inc. | Atomic layer deposition systems and methods including metal beta-diketiminate compounds |
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US20110014797A1 (en) | 2011-01-20 |
US8679913B2 (en) | 2014-03-25 |
KR20100035176A (en) | 2010-04-02 |
WO2009041219A1 (en) | 2009-04-02 |
TWI492301B (en) | 2015-07-11 |
JP5678252B2 (en) | 2015-02-25 |
KR101200577B1 (en) | 2012-11-12 |
KR20110139322A (en) | 2011-12-28 |
CN101971303A (en) | 2011-02-09 |
TW200933738A (en) | 2009-08-01 |
KR101217419B1 (en) | 2013-01-02 |
JPWO2009041219A1 (en) | 2011-01-20 |
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